Impregnating agent



United States Pate ]MPREGNATIN G. AGENT (Arnold Doser; K'oln-MulheixmGermany assignor OFFar- .ttb ntahrike i lav .tA t ng ch -LeverkuseGennannta corporation-o er any No Drawing. Application June 9, 1953SeriabNo. 360,609

. ,CIaim's pi-iority, application-Germany June llp 1952 i .ai {(C-;260:534)

'l he present inventionrelateswtoimpregnating :agents, tespeeially iortextile a materials. :Eurthermore, it concerns a process which- =allows=of rendering; textilev materials or the like'hydrophobic.

laAccording to i the invention textile materials are -.impregnated withaqueoussolutions:or dispersions .of carbamic acids containinghigherlaliphatic hydrocarbon radicals'. Theaqueousssolutionsortdispersions'rnay also contain paraffins, .iwaxes, fats, 1 resinforming zsubstances, salts of polyvalent metals,..s oapst of polyvalentmetals or silicones. The textile materials treated with these solu-,'tions or dispersions are'd-ried at temperatures above 100 1C. Thedrying process may be car-ried out in-two steps, -:yiz., by:pre-dryingthe textile materials at lower temperatures-at about 80-400-C.-a-ndsubsequently drying-'shor'tlyat-about 110 C. or aba-hi'ghertemperature. Another embodiment 'of' the invention consists in dryingtheimpregnated textile materials, rinsing-them with-hot *water and-drying them once more, it-being tobe under- -s'toddthatthetemperature'must'exceed l" C. at least in one dryingstep. {The-carbamicacidscontaining higher aliphatic hydrocarbon radicals -whichare-used-accordingto the present invention, may be obtained in anysuitable-manner, ezg. by reaeting'the addition-products ofalkali metalbisul- "fites and higher aliphatic isocyanates with equivalent amountsof alkali metal hydroxides in anaqueous medium-in*the-'heat vattemperatures not-exceeding 90 C. "The ;term "'*higher aliphatichydrocarbon radicals as Zherein ,used embraces aliphatiehydrocarbonradicals having an uninterrupted chain of at" least eightearbon atoms aswell as radicals -whose carbon chain is interrupted by hetero atoms orgroups ,of hetero atoms.

Theimpregnations obtained according'to thepresent inventiomare fastto.washing and solvents. Hydropho- "-bic effects 'can' be-obtainedbynieans of carbamic acids alone. The water repellent effect is'improvedby the complementarvmse of aqueous ,emulsions ,of paraffin andwaxes; alsosoaps of polyvalent metals may be applied with equaIsuccess.As-the soaps of polyvalent emetals and? the..carbamic,.acids.. easilygive rise. to precipiitates, {the-metahsnaps are preferably appliedafter: using ithe carbamic acids; in this -case thetdrying :step above$100 ;is tpertormed after. the application ofzthe metal 51503135- 1Alternatively, soap maybe added to the. carbamic acids or to theimpregnating baths and the textile material is subsequently-treated:with Water-soluble salts of olyvalent ;me,ta1s,:1forinstancewithaluminumsaltssuch as aluminumnacetate, ,preferably zirconium saltssuch as zirconium oxychloride adjusted to pH 4.0, zirconium acetate orzirconium formate. The treatment with salts of polyvalent metals resultsin an improved impregnating efiect which is retained after washing withsoap or with organic solvents.

The tendency of textile materials to wrinkle and shrink can be reducedby the addition of resin forming substances, such as methylol urea ormelamine methylol ice ,ether, .tojhe carbamicacidsusedaccording totheain- .vention.

. ,Thefollowing, examples serve to, illustrate the invention without,however, limiting itQthereto;temperatures 5 :are in degrees ofeentigrade.

. Example 1 .,is soaked with .theabove emulsion, squeezed. so .thattheincrease in..weight is 60%, heated-to 100 until it is dry andsubsequentlyheated to 120 for a further 5 minutes.

,An excellent waterrepellent effect .is obtained on the material. which.does not disappear even on repeated treatment with gasoline. Theimpregnated material. has a .soft ,feel.

Examplev 2 The emulsion,prepared according to Example 1 is salted 2out:by; means. .of .sodium chlorideand the precipitate is washed with 5%sodium chloridesolution and finally with Water until the filtrate is.free from sodium sulfite. The paste obtained is made into an emulsion at85 byadding 400 cc; of" hot water and the emulsion is filled "up 13literhy adding water of 40.

- Cotton poplin =issoaked with the emulsion obtained, squeezed so thatthe increase in weight is 60%, dried first at 100 and afterwardsheatedto 120 for- 5'minutes. The impregnated fabric is treated with hotwater until it is completely wetted Whereafter it is squeezedand'finally dried at l10l15.

:The' poplin; possesses excellent water repellent properties-whichotherwise can'only be obtained with impregnating agents containingparaifin. The water repellent 40 'eifect is retained-upon= repeatedwashing with gasoline an'd carbon =-tetraehloride.

Example 3 An emulsion is prepared according to'Example 2. Before saltingout, however, 20 g. of an emulsion consist- :ing-of 4.85:g.. ofparaffin, l-.'55-g. of an ester of mon- :tanic acidhaving'thetacid'number 7.5, 0.95- g. of olein having. the acid number 155,0.95 g. of a'44% sodium :hydroxide-solution-and11.7 -cc.- of waterareadded to the ;starting emulsion.

:Cotton poplin is soaked'with this emulsion, squeezed -..so;that theinereaseinweight amounts to 65%, shortly .driedat 60 and thereafterwetted with an emulsion obtained by stirring a-solution of 10 g. ofzirconium toxychloride, :10 cc. of.a 30% acetic acid and 8 g.of-soiudium acetate in SOO-cc. of-water into a solution of5g.-of;..soap;in=550 -cc.-of'water, both solutions having a temperatureof:. The cotton poplin is squeezedagain .:and dried-at 110 for 5minutes.

.Theimaterial possesses a water repellent eifectwhieh -.;=isfastto:organic solvents. It issoft to the touch and ifullerrthan materialtreated-with the emulsion containing no vzirconiumsoap.

5 i'The::application: of zirconium soap is-particularly recommended fortextile material of rayon, cellulose acetate and polyamides.

Example 4 120 for further minutes.

is then cooled to 18.

3 Textile materials are impregnated with the emulsion and squeezed.After that they are treated without drying with a solution of grams ofzirconium oxychloride. in

1 liter ofwater, which is mixed with 15 cc. of 30% acetic acid and 12gramsv of sodium acetate. The textile mate- 'rials are again squeezed,dried at 100 and finally heated to 120 for 5 minutes.

The textile materials are soft and full to the touch and possess anexcellent water repellent effect which is fast to washing with soap andorganic solvents.

Example 5 A.solution of '25 grams of the addition product of stearylisocyanate and sodium bisulfite are dissolved in tained made up to 4liter by the additionof water of 50.

' Cotton poplin is impregnated with the emulsion obtained,.squeezed anddried shortly at 100 and at 115- Thereafter the textile material isrinsed with boiling water until it is completely wetted and dried at110. n

The poplin possesses a very good water repellent effect which isretained after washing five times with gasoline or carbon tetrachloride.

Example 6 An emulsion which contains per liter 25 grams of stearylcarbamic acid and 2 cc. of 30% acetic acid and which is heated to 60 forabout 30 minutes is applied to cotton poplin.

The impregnated material is squeezed so that the increase in weightamounts to 60-70% and dried, first at about 100 and then at 120 for afurther 5 minutes.

The impregnated cotton poplin which is soft and full to the touchpossesses excellent water repellent properties which are fast torepeated washing with the gasoline or carbon tetrachloride.

By rinsing the textile material subsequently with boiling water until itis completely wetted, and drying at a temperature above 110, the waterrepellent efiect is still increased.

The stearyl carbamic acid can be obtained in the following manner:

50 grams of the addition product of sodium bisulfite and stearylisocyanate are dissolved in 500 cc. of water at 85 and, after 10minutes, mixed with 200 cc. of water of within 1 minute, 125 cc. of Insodium hydroxide solution are added to the solution of 70 and thetemperature is kept at 63 for 5 minutes. The emulsion obtained is mixedwith 50 cc. of saturated sodium chloride solution and cooled to Theprecipitate formed is filtered off, washed first with diluted sodiumchloride solution and then shortly with water. The paste obtained isdigested with 6 times the amount of hot water and mixed at 65 inportions with In sodium hydroxide solution until the pH-value of themilky white emulsion is increased to 7.5 and is not lowered again. Theemulsion The pulpy mass is coagulated with saturated sodium chloridesolution, filtered and the residue is washed first with 3% sodiumchloride solution until no sulfite can be detected in the filtrate anylonger, and then with cold water until the filtrate becomes bluish.zirconium hydroxide) in 500 cc. of water of 30.

4 turbid. The reaction product obtained contains 95% of stearyl carbamicacid.

Example 7 Cotton poplin is impregnated with the emulsion, described inExample 2, after addition of 40 grams of dirnethylol urea and 2 cc. of30% acetic acid. The

'poplin is squeezed so that the increase in weight amounts to dried at100 and 135 for 5 minutes.

The poplin is water repellent and distinctly less liable to wrinkling.

Example 8 50 grams of an aqueous paste, which contains 15 grams ofstearyl carbamic acid and 2 grams of the addition product of sodiumbisulfite and stearyl isocyanate, are heated with 200 cc. of water tofor 5 minutes, then diluted with water 'to 500 'cc., and the emulsion isadded slowly with good stirring at 30 to'500 cc. of a -2% solution ofzirconium acetate prepared bydissolving zirconium hydroxide in aceticacid. Rain coat material of cottongabardine is impregnated with theemulsion obtained, squeezed and dried at The'fabric possesses a waterrepellent effect which is retained after repeated treatment withgasoline.

Example 9 40grams of the aqueous paste containing stearyl carbarnic acidof Example 8 are heated with 300 cc. of

.water to 98 and mixed with 160 cc. of an emulsion of .80 which contains25 g. of the paraflin-wax-olein emulsion described in Example 3. Themixture is cooled to '30" and then slowly added withgood stirring toasolution of 12 grams of zirconium acetate (prepared from The pH of theemulsion is brought to 4.0 by means of acetic acid and the emulsion iswarmed at 40.

A poplin fabric of pure cotton is soaked with the emulsion, squeezed anddried, first at 95 and then at 125' for 5 minutes.

The poplin possesses a water repellert effect which is substantiallyretained after washing five times with gasoline and ironing.

Instead of pure cotton fabrics also fabrics containing, besides cotton,30% of rayon, or fabrics of cellulose acetate, wool or natural silkmaybe treated according to the present invention with equal success.Fabrics of polyamide fibers can also be impregnated with the new agentsafter rinsing them with hot water. .All the impregnated fabrics are fulland soft tothe touch. i I claim:

-An impregnating agent comprising stearyl carbamic acid in an aqueousmedium.

References Cited in the file of this patent UNITED STATES PATENTS 72,210,442 -Balle Aug. 6, 1940 2,263,730 Hentrich Nov. 25, 1941 2,442,972Edelstein 'June 8, 1948 2,443,067 Burns June 8, 1948 7 2,468,716 Nyquistet a1 Apr. 26, 1 949 OTHER REFERENCES Chemical Abstractsff vol. 44,1950, pp. 116. I Angewandte Chemie, vol. 59, of 1947 pp. 2571-272.

